Hydroxyalkenylsiloxane rigid urethane foam stabilizers

ABSTRACT

1. A HYDROXYALKYENYLSILOXANE CONSISTING ESSENTIALLY OF (A) AT LAST ONE HYDROXYALKENYLSILOXANE UNIT HAVING THE FORMULA:   (HO-(R)A-R&#39;&#39;-H2C2)B-SI(-(RO)C)-O(4-(B+C)/2)-   WHEREIN R IS A DIVALENT HYDROCARBON GROUP FREE OF ALIPHATIC CARBON TO CARBON MULTIPLE BONDS, R&#39;&#39; IS AN ARYLENE GROUP, A CYCLOALKYLENE GROUP THAT HAS BO HYDROGEN BONDED TO THE CARBON ATOMS ATTACHED TO THE C2H2 GROUP AND THAT IS FREE OF ALIPHATIC CARBON TO CARBON MULTIPLE BONDS OR A DIVALENT -CR2&#39;&#39;&#39;&#39; -GROUP, R&#34; AND R* ARE EACH MONOVALENT HYDROCARBON GROUPS FREE OF ALIPHATIC CARBON TO CARBON MULTIPLE BONDS AND HAVING FROM 1 TO 10 INCLUSIVE CARBON ATOMS, C2H2 IS A -CH=CH-OR A   &gt;C=CH2   GROUP, EACH HYDROXYALKENYLSILOXANE GROUP HAS NO MORE THAN 20 CARBON ATOMS, A HAS A VALUE OF 0 OR 1, B HAS A VALUE OF 1, 2 OR 3, C HAS A VALUE OF 0, OR 2, AND (B+C) HAS A VALUE OF 1, 2 OR 3, AND (B) AT LEAST THREE HYDROCARBYLSILOXANE UNHITS REPRESENTED BY THE FORMULA:   (ROO)D-SI(4-D/2)-   WHEREIN R$$ IS A MONOVALENT HYDROCARBON GROUP FREE OF ALIPHATIC CARBON TO CARBON MULTIPLE BONDS AND HAVING FROM 1 TO 10 INCLUSIVE CARBON ATOMS AND D HAS A VALUE OF 1, 2 OR 3, THE MOLECULAR WEIGHT OF THE SILOXANE PORTION OF THE HYDROXYALKENYLSILOXANE BEING FROM ABOUT 250 TO ABOUT 1300 INCLUSIVE, AND, WHEN DIHYDROCARBYLSILOXANE UNITS, R2 $$ SIO UNITS, ARE PRESENT, THE RATIO OF HYDROXYALKENYLSILOXANE UNITS TO DIHYDROCARBYLSILOXANE UNITS IS AT LEAST 0.5 TO 1.0.

United States Patent Office 3,842,112 Patented Oct. 15, 1974 3,842,112ROXYALKENYLSILOXANE RIGID URETHANE FOAM STABILIZERS George M. Omietanskiand Vincent '1. Chuang, Marietta, Ohio, assignors to Union CarbideCorporation, New York, N.Y. No Drawing. Filed Dec. 29, 1972, Ser. No.319,786 Int. Cl. C07f 7/08 U.S. Cl. 260-448.2 B 9 Claims ABSTRACT OF THEDTSCLOSURE Rigid polyether polyurethane foams are produced commerciallyby introducing several starting materials (i.e., a silicone surfactant,a polyether polyol, a fluorocarbon blowing agent, a catalyst and apolyisocyanate) into a reaction zone. It is important that the relativeamounts of the starting materials in the reaction zone be carefullycontrolled in order to produce a satisfactory polyurethane foam. Controlof the relative amount of the starting materials in the reaction zone isachieved, in part, by forming premixtures containing carefullycontrolled amounts of the silicone surfactant (i.e., asiloxane-polyoxyalkylone block copolymer), polyol, and fluorocarbon. Itis desirable that the various components in these premixtures becompatible so as to eliminate the need for stirring the premixtures toinsure homogeneity. Certain silicone surfactants are more compatiblewith the other starting materials in the premixtures than are othersilicone sur factants. In particular, those silicone surfactants whereinthe polyoxyalkylene blocks are endblocked by hydroxyl groups aregenerally more compatible in premixtures than are silicone surfactantswherein the polyoxyalkylene blocks are endblocked by alkoxy groups.

1Siloxane-polyoxyalkylene block copolymers wherein the polyoxyalkyleneblocks are endblocked by hydroxyl groups are often prepared by theaddition of a linear polyoxyalkylene polymer endblocked at one end by anallyl group and at the other end by a hydroxyl group (or a groupconvertible to a hydroxyl group) with a hydrosiloxane. Suchpolyoxyalkylene reactants can be produced by reacting allyl alcohol withone or more alkylene oxides followed, if desired, by converting thehydroxy group to a group convertible to a hydroxyl group. In theaddition reaction, the SiH groups add to the allyl group to produce theblock copolymer. When the polyoxyalkylene reactant contains an alcoholichydroxyl endblocking group, such groups can also react the some extentwith SiH groups thereby decreasing the content of the desired hydroxylgroups in the block copolymer product with a resulting decrease in thecompatibility of the block copolymer in the above-mentioned premixtures.This side reaction also undesirably increases the viscosity of the blockcopolymer product by partially crosslinking the block copolymer.Further, during the addition reaction, endblocking allyl groups in thepolyoxyalkylene reactant tend to isomerize to some extent to propenylgroups which can react with the hydroxyl endblocking groups of thepolyoxyalkylene reactant or block copolymer to form acetal groups. Theseside reactions also reduce the premixture compatability of the blockcopolymer by decreasing its hydroxyl content and also lead to anundesirable viscosity increase in the block copolymer by partiallycrosslinking the block copolymer.

When the polyoxyalkylene reactant contains an endblocking groupconvertible to a hydroxyl group, the undesirable side reactions of thehydroxyl group with the SiH groups and propenyl groups do not occur butthe undesirable isomerization of allyl groups can still occur and theblock copolymer initially formed must be further processed to regeneratethe hydroxyl groups.

It is an object of this invention to provide hydroxyalkylsiloxanes thatare useful as foam stabilizers for rigid polyether polyurethane foams.

It is an object of this invention to provide hydroxyalkylsiloxanes thatare useful as foam stabilizers for rigid polyether polyurethane foamsand that are readily produced from relatively simply alcohol reactants.

It is an object of this invention to provide hydroxyalkylsiloxanes thatare useful as foam stabilizers for rigid polyether polyurethane foamsand that are produced by process relatively free of undesirable sidereactions.

Other objects of this invention will be apparent from the descriptionthereof appearing below.

This invention provides hydroxyalkenylsiloxanes consisting essentiallyof: (A) at least one hydroxyalkenylsiloxane unit having the formula:

[HO( )u 'C2H2]- 0 wherein -R is a divalent hydrocarbon group free ofaliphatic carbon to carbon multiple bonds, R is an arylene group, acycloalkylene group that has no hydrogen bonded to the carbon atomattached to the C H group and that is free of aliphatic carbon to carbonmultiple bonds or a divalent- CR "-group R" and R are each monovalenthydrocarbon groups free of aliphatic carbon to carbon multiple bonds andhaving from 1 to 10 inclusive carbon atoms, C H is a CH=CH or a group,each hydroxyalkenylsiloxane group has no more than 20 (preferably nomore than 10) carbon atoms, a has a value of O or 1, b has a value of 1,2 or 3, c has a value of 0, 1 or 2, and (b.+c) has a value of 1, 2 or 3;and (B) at least three hydrocarbylsiloxane units represented by theformula:

R SiO T wherein R is a monovalent hydrocarbon group free of aliphaticcarbon to carbon multiple bonds and having from 1 to 10 inclusive carbonatoms and d has a value of 1, 2 or 3, the molecular weight of thesiloxane portion of the hydroxyalkenylsiloxane being from about 250 toabout 1300 inclusive, and, when dihydrocarbylsiloxane units (R SiOunits) are present, the ratio of hydroxyalkenylsiloxane units todihydrocarbylsiloxane units is at least 0.5 to 10. Those of thehydroxyalkenylsiloxanes of this invention containing at least onehydroxyalkenylsiloxane unit represented by formula (I) above whereinb-i-c is 1 or 2 are stable in premixtures containing the siloxane, apolyol and a blowing agent and so such siloxanes are preferred.Preferably, the siloxane portion represents from 60 to weight percent ofthe hydroxyalkenylsiloxane and the hydroxyalkenylsiloxane has aviscosity up to 5000 centistokes at 25 C. As used herein, the siloxaneportion of the hydroxyalkenylsiloxane includes all of the groups andatoms in the hydroxyalkenylsiloxane apart from the hydroxyalkenylgroups, i.e., apart from the HO(R) R'CH=CH groups A preferred class ofthe hydroxyalkenylsiloxanes of this invention are represented by theaverage formula:

H O C Rz C 2H MegSiO (MeSiO)X(MezSiO) SiMc (III) wherein R' is a methylor ethyl group, Me is a methyl group, x has a value from 1 to 8inclusive, y has a value from 1 to 6 inclusive, the molecular weight ofthe hydroxyalkenylsiloxane, exclusive of the hydroxyalkenyl groups, isfrom about 300 to about 1000 inclusive and xzy is at least 0511.

Typical of the monovalent hydrocarbon groups free of aliphatic carbon tocarbon multiple bonds represented by R, R", R and R in formulas (I),(II) and (III) above are the alkyl groups (for example the methyl,ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, isobutyl, t-butyl,n-octyl and decyl, groups), the cycloalky groups (for example, thecyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptylgroups), the aryl groups (for example, the phenyl and naphthyl groups),the aralkyl groups (for example, the benzyl, 2-phenyl-ethyl,2-phenylpropyl, cumyl groups), and the alkaryl groups (for example, thetolyl, t-butylphenyl and styryl groups). Typical of the divalenthydrocarbon groups represented by R in formula (I) above are thealkylene and arylene groups (e.g., the methylene, ethylene, propylene,cyclohexylene and phenylene groups). Typical of the cyclic divalenthydrocarbon groups free of aliphatic carbon to carbon multiple bondsrepresented by R in formula (I) above are the arylene groups such as thephenylene and tolylene groups and the cycloalkylene groups such as:

S and 13/ OH;

This invention still further provides a process for producing thehydroxyalkenylsiloxanes described above which process comprises reacting(1) an acetylenic alcohol represented by the formula:

HO(R),,RCECH (IV) wherein the symbols are as defined for formula (I)with (2) a hydrosiloxane consisting essentially of (A) at least onesiloxane unit having the formula:

i HbS1O 2 (V) wherein the symbols are as defined for formula (I), and(B) at least three units having formula (II) above, the molecular weightof the hydrosiloxane being from 250 to 1300 inclusive, in the presenceof (3) a catalyst for the addition of SiH to olefinic bonds. Whenhydroxyalkylsiloxanes of this invention containing dihydrocarbylsiloxaneunits are produced, the hydrosiloxane reactant must have a ratio ofhydrosiloxane units to dihydrocarbylsiloxane units of at least 0.5 to 1.

Typical of the acetylenic alcohols that are useful in producing thehydroxyalkenylsiloxanes of this invention are the following:

3-hydroxy-3-methyl-1-but yne H C E C M92 0 H C E CH C 5 CHl-hydroxy-Lethynyl cyclohexane S Propargyl alcohol HC 5 CCH2OH Thehydrosiloxane reactants used to produce the hydroxyalkenylsiloxanes ofthis invention can be produced by cohydrolyzing and cocondensing theappropriate hydrolyzable silanes or by equilibrating appropriate siloxanes using conventional techniques.

The process for producing the hydroxyhydroalkenylsiloxanes of thisinvention is conducted in the same manner as used in producing knownhydrosiloxane-alkyne adducts (i.e., at elevated temperatures and in thepresence of a catalyst). Since relatively little side reactions occur,approximately stoichiometric amounts of the olefinic alcohol and thehydrosiloxane (one acetylenic group per SiH group) can be employed.Solvents for the alcohol and hydrosiioxane reactants (e.g., liquidhydrocarbons such as toluene) can be employed. Amounts of platinumcatalysts that provide from 10 to 200 parts by Weight of platinum permillion parts by weight of the reactants are useful. Suitable reactiontemperatures are from 50 C. to C. Suitable addition catalysts includechloroplatinic acid and complexes thereof and elemental platinumsupported on charcoal or gamma alumina. At the conclusion of theprocess, any residual (unreacted) SiH can be removed by adding a smallamount of methanol and sodium bicarbonate to the product and heating.

In view of the fact that the acetylenic bonds in the acetylenic alcoholreactants used in producing the siloxanes of this invention do notisomerize during the reaction with hydrosiloxanes and do not undergoother side reactions significantly, the resulting product containslittle undesirable byproducts. Another advantage of this process is thatit involves the use of monomeric alcohol reactants as distinguished fromthe polyoxyalkylene alcohol reactants employed in prior art processes.Further, the monomeric alcohol reactants employed in the process of thisinvention need not be reacted to block the hydroxy groups as is done insome prior art processes involving the use of polyoxyalkylene alcoholreactants.

This invention also provides a method for producing rigid polyurethanefoams by reacting and foaming a foam formulation (reaction mixture)comprising (a) a polyether containing at least two hydroxyl group andhaving a hydroxyl number from about 200 to about 1000, (b) an organicpolyisocyanate, (c) a catalyst for the reaction of (a) and (b) toproduce the polyurethane, (d) a blowing agent and (e) a novelhydroxyalkenylsiloxane as described above as a foam stabilizer.

The polyethers that are useful in producing rigid polyurethane foam inaccordance with this invention include polyoxyalkylene polyols includingalkylene oxide adducts of, for example, glycerol, 1,2,6-hexanetriol,1,1,l-trimethylolethane, 1,1,l-trimethylolpropane, pentaerythritol, sorbitol, sucrose, lactose, alpha-methylglucoside, alphahydroxyalkylglucoside, ammonia, triethanolamine, triisopropanolamine,ethylenediamine, diethylenetriamine, novolac resins, phosphoric acid,benzenephosphoric acid, polyphosphoric acids such as tripolyphosphoricacid and tetrapolyphosphoric acid, phenol aniline formaldehyde ternarycondensation products, aniline formaldehyde condensation products, andthe like, are useful. The alkylene oxide employed in producingpolyoxyalkylene polyols normally have from 2 to 4 carbon atoms.Propylene oxide and mixtures of propylene oxide with ethylene oxide arepreferred.

The hydroxyl number of the polyether polyols in producing polyurethanefoams in accordance with this in vention can range from about 200 toabout 1000. The hydroxyl number is defined as the number of milligramsof potassium hydroxide required for the complete neutralization of thehydrolysis product of the fully acetylated derviative prepared from 1gram of polyol.

The hydroxyl number can also be defined by the equation:

56.1 X 1000 Xf where OI-I=hydroxyl number of the polyol The organicpoly-isocyanates that are useful in producing polyurethane foams inaccordance with this invention are organic compounds that contain atleast two isocyanato groups. Suitable organic polyisocyanates includethe poly(aryleneisocyanates) and the hydrocarbon diisocyanates, (e.g.,the alkylene diisocyanates and the arylene diisocyanates) Illustrativeof suitable polyisocyanates are Suitable poly(aryleneisocyanates)include polymethylene poly(phenyleneisocyanates) having the formula:

NCO

wherein x has an average value from 1.1 to 5 inclusive (preferably from2.0 to 3.0).

The catalysts that are useful in producing polyurethane foams inaccordance with this invention include amine catalysts and metalcatalyst. Useful amine catalysts include tertiary amines such asN-N-dimethyl-Z-[Z-dimethylaminoethoxy]ethylamine, trimethylamine,N-methylmorpholine, N-ethylmorpholine, N,N-dimethylbenzylamine, N,Ndimethylethanolamine, N,N,N,N-tetramethyl-l,3-butanediamine,triethanolamine, 1,4-diazabicyclo [2,2,2] octane (triethylenediamine),hexadecyldimethylamine, and the like. Useful metal catalysts includedibutyl tin dilaurate.

Blowing agents that are useful in producing polyurethane foam inaccordance with this invention include Water, halogenated hydrocarbons(e.g., fluorocarbons), such as trichloromonofiuoromethane,dichlorodifiuoroclo[2,2,2 octane (triethylenediamine)hexade-cyldimethylmethane, dichloromonofluoromethane, dichloromethane,trichloromet h-ane, l,l-dichloro-l-fluoroethane, 1,1,2-trichloro 1,2,2trifluorometh-ane, hexafluorocyclobutane, octafiuorocyclobutane, and thelike. Another class of blowing agents include thermally-unstablecompounds which which liberate gases upon heating, such asN,N-dimethyl-N,N'-dinitrosoterephthal'amide and the like.

The relative amounts of the various components used in producingpolyurethane foams in accordance with this invention are not narrowlycritical. The polyether polyol and the polyisocyanate, taken together,are present in the foam formulations (reaction mixtures) used to producesuch foams in a major amount. The relative amounts of these twocomponents is the amount required to produce a polyurethane structure ofthe foam and such relative amounts are well known in the art. Theblowing agent and catalyst are each present in the known amountnecessary to achieve the function of the component. Thus, the blowingagent is present in a minor amount suflicient to foam the reactionmixture to the desired density and the catalyst is present in acatalytic amount (i.e., an amount sufiicient to catalyze the reaction toproduce the polyurethane at a reasonable rate). The siloxane is presentin a foam-stabilizing amount (i.e., in an amount sufiicient to stabilizethe foam). The silox-ane is preferably employed in an amount of from 0.2to 5.0 parts by weight per parts by weight of the polyol,po'lyisocyanate, catalyst and siloxane.

Conventional additives can be employed in minor amounts in producingpolyurethane foams in accordance with the process of this invention ifdesired for specific purposes. Such additives include inhibitors (suchas alpha-methyl styrene and alloocimene) and flame retardants (such asFyrol-6).

If desired, mixtures of the above-described starting materials (i.e.,polyols, polyisocyanates, etc.) can be used in producing polyurethanefoams in accordance with this invention.

In accordance with this invention, polyurethane foams are produced bythe conventional procedures such as the one-step or one-shot techniquewherein all of the reactants are reacted simultaneously with the foamingoperation. The foaming and the urethane-foaming reaction in the one-steptechnique occur without the application of external heat. Thereafter,the foam can be heated (postcured) at F. to 212 F. to eliminate anysurface tackiness if desired. Preferred novel siloxanes and premixturecontaining the novel siloxanes are of low viscosity and do not presentparticular problems when pumped into mixing headings in the techniqueconventionally used in the oneshot process. It is often convenient toprepare premixtures containing the hydroxyalkylsiloxane, the blowingagent and the polyol. Such premixtures can also contain the catalystsand/or other additives.

The rigid polyurethane foams produced in accordance with this inventioncan be used for the same purposes as conventional rigid polyetherpolyurethane foams (e.g., they can be used as thermal insulatingmaterials in buildings and in refrigerators).

The hydroxyalkenylsiloxanes of this invention are also useful aslubricants for textile fibers, emulsifiers and wetting agents.

In the above formula, the symbols representing the numbers and types ofgroups need not have the same meaning at each occurrence throughout thecomposition. For example, some of the groups represented by formula (II)above can be dimethylsiloxane (Me SiO) while other of such groups can betriethylsiloxane groups Other hydroxy-organosiloxane rigid polyurethanefoam stabilizers are disclosed in US. Pat. application No. 319,- 528,filed Dec. 29, 1972, in the names of G. M. Omietanski, H. D. Furbee andV. T. Chuang entitled Hydroxybicyclosiloxane Rigid Urethane FoamStabilizers and in US. Patent Application Serial No. 319,788, filed Dec.29, 1972, names of G. M. Omietanski and V. T. Chuang, entitledHydroxyalkylsiloxane Rigid Urethane Foam Stabilizers.

The following Examples illustrate the present inveution.

In the following Examples, the abbreviations and symbols used have theindicated meanings:

cc: cubic centimeters cstks: viscosity in centistokes at C.

Et: ethyl Fyrol-G: Diethyl-bis(2 hydroxyethyl)amino methylphosphonateg.: grams gal.: gallon I.R.: infra red lbs.: pounds Me: methyl ml.:milliliter min.: minute WM: molecular weight NMR: Nuclear MagneticResonance Percent: percent PAPI: A polymeric polyisocyanate having theaverage formula:

NCO

HYDROSILOXANE PREPARATION The following procedure is illustrative of amethod that can be employed in making the hydrosiloxane reactants usefulin producing the hydroxyalkenylsiloxanes of this invention. A solutionof 0.0218 moles of a hydrosiloxane having the nominal formula Me SiOMeHSiO SiMe (55.1 g., 354 cc./g. SiH), 0.909 moles of a mixture ofhexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane (63.6 g.)and 0.193 moles of hexamethyldisiloxane (31.4 g., 99.8%) Were reacted inthe presence of 3.0 g. sulfuric acid (reagent grade) for 4 hours. Thissolution was then neutralized with sodium bicarbonate and filtered togive a water white clear equilibrated filtrate with a nominal formula ofa viscosity of 4.2 centistokes and a silanic hydrogen content of 129cc./g.

The above described reactions were carried out in a 500 m1.,three-necked round bottom Morton flask equipped with a stirrer and twoglass stoppers. The above nominal formula for this hydrosiloxane is thetheoretical formula calculated on the basis of complete reaction of thesiloxane starting materials. In this instance, the nominal formula is inagreement with the experimentally measured silanic hydrogen content ofthe hydrosiloxane. In the case of those of the hydrosiloxanes describedbelow where the experimentally measured silanic hydrogen contents didnot agree with the nominal formulas, the nomina formulas were correctedto agree with the silanic hydrogen measurement and the correctedformulas appear below. 5

8 CATALYST SOLUTIONS The chloroplatinic acid used in producing thehydroxyalkenylsiloxanes described below was employed in the form of asolvent solution. The solution contained 3.3 or 10 parts by weight ofchloroplatinic acid hexahydrate and 96.7 or parts by weight of a mixtureof solvents. The mixture of solvents consisted of 90 weight percent ofthe dimethyl ether of ethylene glycol and 10 weight percent of ethanol.

EXAMPLE I A solution of 0.308 moles of 3-hydr0xy-3-methy1-lbutyne(dimethyl propargyl alcohol) (26.3 g., 98.3% purity, pH of 7.0) and ahydrosiloxane having the average formula Me SiO(Me SiO) (MeHSiO)- SiMe(0.28 equivalents of SiH, 36.3 g., 173 cc./g. SiH, 7.2 (cstks.) werereactad in the presence of 0.08 cc. of 10 wt.-percent chloroplatinicacid solution parts by weight of platinum per million parts by weight ofreactants) to give an adduct of the average formula of and a viscosityof 30,898 cstks. The reaction was carried out in a 250 ml., three-neckedround bottom flask fitted with a stirrer, thermometer, Dean-Stark trap,sparge tube and a condenser. The solution, under a nitrogen sparge wasmixed and heated to 60 C. and catalyzed. Further heating to 91 C.resulted in an exotherm which was controlled. Additional heating at 100C. was maintained until the hydrosilation was completed (as evidenced bythe absence of hydrogen in the silicon hydride-alcoholic potassiumhydroxide fermentation tube test). The solution was then lites strippedat 100 C. under a nitrogen sparge. Total preparation time was 22.5hours.

EXAMPLE II Employing the procedure used in Example I 0.272 moles of thesame acetylenic alcohol (23.3 g., 98.3% purity, pH of 7.0) was reactedwith a hydrosiloxane with nominal formula Me siOtMe Sio) (MeHSiO) SiMe(0.259 equivalents of SiH, 45.0 g., 129 cc./g. SiH, 4.2 cstks.) in thepresence of 1.12 cc. of 3.3 wt. percent chloroplatinic acid solution(200' parts by Weight of platinum per million parts by weight ofreactants) to give an adduct with the average formula and a viscosity of1,661 cstks. I.R. analysis indicated the presence of a hydroxylfunctionality at 3.0 microns which is consistent with the above formula.

EXAMPLE III Using the procedure described in Example I, 0.218 moles ofHCECCMCZOH (18.6 g., 98.3 wt.-percent, pH of 7.0) was added (0.211equivalents of SiH, 43.8 g., 102 cc./g. SiH, 4.2 cstks.) with 0.08 cc.of 10 wt. percent chloroplatinic acid solution (100 parts by weight ofplatinum per million parts by weight of reactants) present. Theresultant product mainly had an average formula of and a viscosity of405 cstks. The presence of OH absorp tion at 3.0 microns, as determinedby IR. analysis is consistent with the above average formula.

EXAMPLE 1V For purposes of comparison and using the procedure describedin Example I, 0.219 moles of HCECCMe OH (18.7 g., 98.3% purity, pH of7.0) was added to Me SiO (MeHSiO SiMe 9 (0.173 equivalents of SiH, 38.8g., 98.9% purity) in the presence of 0.14 cc. of wt.-percentchloroplatinic acid solution (100 parts by weight of platinum permillion parts by weight of reactants). This addition resulted mainly inthe following adduct:

Me SiO[HOCMe CH= CHSiMeO 1 SiMe NMR analysis confirmed that the producthad a ratio of two terminal adduct (trans) to one internal adduct andalso indicated that no side reaction (i.e., SiH+COH) had occurred. Theviscosity of this adduct Was 11.8 cstks. and LR. analysis indicated thatpresence of OH absorption at 3.0 microns which is also consistent withthe above formula.

EXAMPLE V Employing the procedure described in Example I, 0.196 moles of3-hydroxy-3-methyl-l-pentyne (20.0 g., 99.9%

purity, pH of 7.0) was reacted with a hydrosiloxane hav ing the nominalformula Me SiO(Me SiO) (MeI-ISiO) SiMe (0.194 equivalents of SiH, 42.6g., 102 cc./g. SiH, 4.2 cstks.) in the presence of 0.05 cc. of a 3.3wt.-percent chloroplatinic acid solution (10 parts by weight of platinumper million parts by weight of reactants) as the catalyst to give aproduct which has the average formula of Me SiO (Me SiO) 4[HOCMeEtCH:CHSiMeO] 2. SiMe and a viscosity of 262 cstkS. The presenceof OH absorption at 3.0 microns, as determined by IR. analysis isconsistent with the average structural formula.

EXAMPLE VI For purposes of comparison and employing the proceduredescribed in Example I, 0.157 moles of 3-hydroxy-3-methyl-1-butyne (13.4g., 98.3% purity pH of 7.0) was added to Me SiOSiMe H (0.149 equivalentsof SiH, 24.0 g., 91.6%) in the presence of 0.03 cc. of a 3.3 wt.-percentchloroplatinic acid solution (10 parts by weight of platinum per millionparts by weight of reactants). This addition resulted in an adduct withthe formula: Me SiO[SiMe CH=CHMe COH]. The presence of OH absorption at3.0 microns as determined by I.R. analysis is consistent with thenominal formula.

The structure and properties of the hydroxyalkenylsiloxanes produced asdescribed in Examples I to VI above are tabulated in Table I below.

1 M denotes IVIGQSiOO-5, D denotes Me SiO, D denotes HO CMegOH=CH SiMeO,D denotes HOCMeEtCH- CHSiMeO, M denotes HOCMBQCH =CHSiMe OM.

2 siloxane denotes the portion of the product exclusive of thelggirohydrovalkenyl (i.e., the HO CMe CH=CH and HOCMeEtCH:

oup

3 No a hydroxyalkenylsiloxane of this invention. Presented only forpurposes of comparison. 7

4 A commercially available siloxane-polyoxyalkylene block copolymerrigid polyether polyurethane foam stabilizer. Not a hydroalkenylsiloxaneof this invention. Presented only for purposes of comparison.

10 EXAMPLE VII The siloxanes produced as described in Examples I to VIabove were used in producing polyurethane foams using the formulationand foaming procedure described below.

Foaming procedure A cleaned and waxed mold was heated to 212 F. and anyexcess wax was removed with a clean cloth. A premixture was formedcontaining the Fyrol6, Polyol I, TMBDA and Ucon-ll. The premixture wasthoroughly mixed until completely homogeneous and any Ucon-ll thatvolatilized during mixing was replaced. The mold is cooled to about F.The siloxane is added to the premixture and the premixture is againmixed for 10 seconds. Then the Papi is added to the premixture and theresulting formulation is mixed for 8 seconds. The formulation isintroduced into the mold which is then closed. The temperature of themold is maintained at 115 to F. for 5 minutes. Then the mold is placedinto a 212 F. oven for 5 minutes. The cured foam is then removed fromthe mold. A slice is cut from the center of the foam and the number ofcells per linear inch in the middle of the slice is measured.

The latter measurement is an index of the fineness of the cellstructure. A foam having fewer than 26 cells per inch is regarded asunsatisfactory (coarse). The Rise or height of the foam is measured. Inview of the fact that the formulation used to produce the foam isviscous, a portion thereof sticks to the Walls of the container in whichthe formulation is formed when the bulk of the formulation is introducedinto the mold. Accordingly, the foam is weighed and the measured rise iscorrected to allow for the amount of the formulation retained in thecontainer by using the following formula:

Corrected Rise: [10 )(firmulLWeigE 1Q] foam weight [Measured Rise]Premixture compatibility test A mixture is formed containing thefollowing materials:

840 grams Polyol I 360 grams Fyrol-6 18 grams TMBDA 600 grams Ucon-l lThe mixture is stirred at moderate speed with an air motor equipped witha 2 inch propeller. Any Ucon-ll that evaporates during the mixing isreplaced by adding more Ucon11 to the mixture. A 75.8 gram sample of themixture so formed is added to a jar and then 0.5 cubic centimeters of ahydroxyalkenylsiloxane is added to the jar to form a premixture. Thepremixture is maintained at a temperature below 23 C. to minimize lossof Ucon-ll by volatilization. The premixture is stirred with a spatulauntil well mixed and is then observed visually for clarity oropaqueuess.

The results of the above foam preparations are shown in Table II below:

TABLE II.-TEST RESULTS a Not a hydroxyalkenylsiloxane of this invention.Presented only for purposes of comparison.

b See footnote 4 to Table I above.

The poor foams obtained using the hydroxyalkenylsiloxanes of Examples IVand VI illustrate the importance of the siloxane molecular weightlimitations that characterize the hydroxyalkylsiloxanes of thisinvention. The siloxanes of Examples IV and VI had siloxane molecularweights of less than 250.

In the above Examples, the formula of the principal (terminal or trans)adduct product is shown. Some of the isomeric (internal) adduct was alsoproduced in each case.

What is claimed is:

1. A hydroxyalkyenylsiloxane consisting essentially of (A) at least onehydroxyalkenylsiloxane unit having the formula:

wherein R is a divalent hydrocarbon group free of aliphatic carbon tocarbon multiple bonds, R is an arylene group, a cycloalkylene group thathas no hydrogen bonded to the carbon atom attached to the C H group andthat is free of aliphatic carbon to carbon multiple bonds or a divalent-CR group, R" and R are each monovalent hydrocarbon groups free ofaliphatic carbon to carbon multiple bonds and having from 1 to 10inclusive carbon atoms, C H is a -CH=CH- or a group, eachhydroxyalkenylsiloxane group has no more than 20 carbon atoms, a has avalue of or 1, b has a value of 1, 2 or 3, c has a value of 0, 1 or 2,and (b+c) has a value of 1, 2 or 3; and (B) at least threehydrocarbylsiloxane units represented by the formula:

wherein R is a monovalent hydrocarbon group free of aliphatic carbon tocarbon multiple bonds and having from 1 to inclusive carbon atoms and dhas a value of 1, 2 or 3, the molecular weight of the siloxane portionof the hydroxyalkenylsiloxane being from about 250 to about 1300inclusive, and, when dihydrocarbylsiloxane units, R SiO units, arepresent, the ratio of hydroxyalkenylsiloxane units todihydrocarbylsiloxane units is at least 2. A hydroxyalkenylsiloxane asclaimed in claim 1 wherein each hydroxyalkylenylsiloxane group has nomore than 10 carbon atoms, the siloxane portion represents from 60 toweight percent of the hydroxyalkenylsiloxane and thehydroxyalkenylsiloxane has a viscosity up to 5000 centistokes at 25 C.

3. A hydroxyalkylsiloxane as claimed in claim 1 containing at least onehydroxyalkenylsiloxane unit as defined in claim 1 wherein b+c is 1.

4. A hydroxyalkenylsiloxane as claimed in claim 1 containing at leastone hydroxyalkenylsiloxane unit as defined in claim 1 wherein b+c is 2.

5. A hydroxyalkenylsiloxane as claimed in claim 1 represented by theaverage formula:

HO 0 Rz CgH MegSiOOZliO),(MezSiO),SiMe

wherein R is a methyl or ethyl group, Me is a methyl group, x has avalue from 1 to 8 inclusive, y has a value from 1 to 6 inclusive, themolecular weight of the hydroxyalkenylsiloxane, exclusive of the'hydroxyalkenyl groups, is from about 250 to about 1300 inclusive andxzy is at least 0.5:1.

6. A process for producing a hydroxyalkenylsiloxane as claimed in claim1 which process comprises reacting (1) an acetylenic alcohol representedby the formula:

HO (R) R -CE'CH wherein the symbols are as defined in claim 1 with (2) ahydrosiloxane consisting essentially of (A) at least one siloxane unithaving the formula:

wherein the symbols are as defined in claim 1 and (B) at least threehydrocarbylsiloxane units as defined in claim 1 above, the molecularweight of the hydrosiloxane being from 250 to 1300 inclusive and, when ahydroxyalkenylsiloxane containing dihydrocarbylsiloxane units is beingproduced, the ratio of hydrosiloxane units to dihydrocarbylsiloxaneunits in the hydrosiloxane is at least 0.5 to 1 in the presence of (3) acatalyst for the addition of SiH to olefinic bonds.

7. A process as claimed in claim 6 wherein the alcohol is present in anamount that provides about 1 olefinic group per SiH of thehydrosiloxane.

8. A process as claimed in claim 6 wherein the catalyst is a platinumcatalyst.

9. A process as claimed in claim 6 wherein the catalyst ischloroplatinic acid.

References Cited UNITED STATES PATENTS 2,970,150 1/1961 Bailey 260-448.2E 2,823,218 2/1958 Speier et al 260448.2 E 3,317,460 5/1967 Clark et al.260448.2 BX 2,920,093 l/ 1960 Bailey 260448.2 Q 2,837,550 6/1958 Prober260448.2 B

DANIEL E. WYMAN, Primary Examiner P. F. SHAVER, Assistant Examiner U.'S.Cl. X.R.

26025 AH, 448.2 B, 448.2 Q

u miss simss swam" 0mm:

Patent n0. 3,842,112 was October 15 1974 Inventor) so M. Omietanski & v.T. Chuang It is certified that QYEOE ass-sets is the sbeve ifientifiedpatent and that said Letters ?atent are heresy sotiectefi as shownbelow:

Column 3, delete line 23 and substitute --ample, the tolyl andt-butylphenyl groups) Typical-- Column 4, line 75 after "m.w." insert anequal sign Column 7, line 49, delete "0.909 moles of" I I Signed andseeied this 8th day of Februa t'y Z975.

(SEAL) Attest:

C. MARSHALL DANN RUTH Ca MASON Commissioner of Patents Attesting Officerand Trademarks

1. A HYDROXYALKYENYLSILOXANE CONSISTING ESSENTIALLY OF (A) AT LAST ONEHYDROXYALKENYLSILOXANE UNIT HAVING THE FORMULA: